EP0083137B1 - Aqueous, oxidatively drying coating composition - Google Patents
Aqueous, oxidatively drying coating composition Download PDFInfo
- Publication number
- EP0083137B1 EP0083137B1 EP82201642A EP82201642A EP0083137B1 EP 0083137 B1 EP0083137 B1 EP 0083137B1 EP 82201642 A EP82201642 A EP 82201642A EP 82201642 A EP82201642 A EP 82201642A EP 0083137 B1 EP0083137 B1 EP 0083137B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyd resin
- acid
- coating composition
- weight
- oxidatively drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000001035 drying Methods 0.000 title claims abstract description 52
- 239000008199 coating composition Substances 0.000 title claims abstract description 39
- 229920000180 alkyd Polymers 0.000 claims abstract description 77
- 239000002253 acid Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 7
- 239000002023 wood Substances 0.000 abstract description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 abstract 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 23
- 239000011541 reaction mixture Substances 0.000 description 22
- 235000014113 dietary fatty acids Nutrition 0.000 description 18
- 229930195729 fatty acid Natural products 0.000 description 18
- 239000000194 fatty acid Substances 0.000 description 18
- 239000003999 initiator Substances 0.000 description 17
- 150000004665 fatty acids Chemical class 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 15
- 239000008096 xylene Substances 0.000 description 15
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229960002887 deanol Drugs 0.000 description 5
- 239000012972 dimethylethanolamine Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 235000019485 Safflower oil Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000003813 safflower oil Substances 0.000 description 3
- 235000005713 safflower oil Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- XZRHNAFEYMSXRG-UHFFFAOYSA-N 2,5-dimethylbenzoic acid Chemical compound CC1=CC=C(C)C(C(O)=O)=C1 XZRHNAFEYMSXRG-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- RZJGICAQAAMOFI-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(3-ethoxy-2,4-dihydroxyphenyl)methanone Chemical compound CCOC1=C(O)C=CC(C(=O)C=2C(=CC(O)=CC=2)O)=C1O RZJGICAQAAMOFI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- GBURUDXSBYGPBL-UHFFFAOYSA-N 2,2,3-trimethylhexanedioic acid Chemical compound OC(=O)C(C)(C)C(C)CCC(O)=O GBURUDXSBYGPBL-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JMUKALCRCFJQTI-UHFFFAOYSA-N 2-(7-carboxyheptyl)-5-hexylcyclohex-3-ene-1-carboxylic acid Chemical compound CCCCCCC1CC(C(O)=O)C(CCCCCCCC(O)=O)C=C1 JMUKALCRCFJQTI-UHFFFAOYSA-N 0.000 description 1
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical class OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 1
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- SMNNDVUKAKPGDD-UHFFFAOYSA-N 2-butylbenzoic acid Chemical compound CCCCC1=CC=CC=C1C(O)=O SMNNDVUKAKPGDD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- BHEIMYVOVVBWRL-UHFFFAOYSA-N 2-methyl-2-phenylpropane-1,3-diol Chemical compound OCC(C)(CO)C1=CC=CC=C1 BHEIMYVOVVBWRL-UHFFFAOYSA-N 0.000 description 1
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- RYKIXDBAIYMFDV-UHFFFAOYSA-N 5-(7-carboxyheptyl)-2-hexylcyclohex-3-ene-1-carboxylic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)CC1C(O)=O RYKIXDBAIYMFDV-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- PJUKKJYOSBWEQO-UHFFFAOYSA-L barium(2+);octanoate Chemical compound [Ba+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O PJUKKJYOSBWEQO-UHFFFAOYSA-L 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- AUDHXKAOPMTYES-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 AUDHXKAOPMTYES-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- ASJCSAKCMTWGAH-UHFFFAOYSA-N cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCC1C(O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- JXNPEDYJTDQORS-UHFFFAOYSA-N linoleyl alcohol Natural products CCCCCC=CCC=CCCCCCCCCO JXNPEDYJTDQORS-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
Definitions
- the invention relates to an aqueous, oxidatively drying coating composition based on a binder system obtained by polymerization of one or more monoethylenically unsaturated compounds in the presence of an aqueous solution of an ionized, oxidatively drying alkyd resin.
- a coating composition of the type indicated above is known from US Patent Specification 4116 903.
- the gloss of the final coating and the brushability and properties such as hiding power, workability and filling of surface irregularities in the substrate, which are connected with a low solids content, are not quite satisfactory.
- An object of the present invention is to provide a coating composition which guarantees an optimum combination of said properties while retaining the other desired properties.
- the composition may display a very good hydrolytic resistance.
- the coating composition according to the invention is characterized in that per 100 parts by weight (calculated on solid matter) the binder system also contains 5 ⁇ 65 parts by weight (calculated on solid matter) of a dispersed, oxidatively drying alkyd resin having a number average molecular weight in the range of 600-6 000, a viscosity not higher than 30 Pa.s, measured at 20°C, an acid number of 0-20 and a hydroxyl number of 0 ⁇ 130, which is substantially built up of 3 ⁇ 40% by weight of a hydroxyl compound having 2-8 hydroxyl groups, 2-44% by weight of a di- and/or multivalent carboxylic acid, of which 20-100 mole % is a cycloaliphatic dicarboxylic acid, and 20-90% by weight of an ethylenically unsaturated monocarboxylic acid having 6-24 carbon atoms.
- the ionized, oxidatively drying alkyd resin may be prepared by polycondensation of generally one or more aliphatic and/or cycloaliphatic di- and/or multivalent and, if desired, monovalent alcohols with one or more aliphatic, cycloaliphatic and/or aromatic di- and/or multivalent and, if desired, monovalent carboxylic acids, and/or derivatives of such alcohols or carboxylic acids, such as epoxy compounds, esters or acid anhydrides.
- Alcohols that are preferably used are the compounds of the formula HOCH 2 -CR,CR 2 -CH 2 0H, where R 1 represents a -CH 2 0H group, a group R 2 or an acryloyl group or methacryloyl group, and R 2 represents a hydrocarbon group carrying an inert substituent or not, for instance an alkyl group having 1-4 carbon atoms, an aryl group having 6-14 carbon atoms, chloromethyl, nitropropyl or p-acetophenyl.
- Representative alcohols that are preferably used are: trimethylol ethane, trimethylol propane, trimethylol butane, 2,2-dimethyl-1,3-propane diol, 2-methyl-2-propyl-1,3-propane diol, 2-ethyl-2-butyl-1,3-propane diol and 2-methyl-2-phenyl-1,3-propane diol. More particularly, use is made of trimethylol propane.
- the preferably employed alcohols are generally used in an amount of 2-98 mole %, more particularly 2-90 mole %, of the total amount of hydroxyl group-containing compounds to be subjected to polycondensation.
- suitable alcohols further include: 1,2-propylene glycol, propylene oxide, 1,4-dimethylol cylcohexane, perhydrobisphenol, glycerol, glycidol, pentaerythritol and etherification products of polyvalent alcohols, for instance: di-, tri-, tetra- and a polypentaerythritol.
- suitable di- or polyvalent carboxylic acids may be mentioned: succinic acid, adipic acid, trimethyl adipic acid, sebacic acid, dimerised fatty acids, tetrahydrophthalic acid, 3,6-endomethylene tetrahydrophthalic acid, 3,6-endomethylene cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid or a homologue thereof, 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, orthophthalic acid, isophthalic acid, terephthalic acid and trimellitic acid.
- one or more of these acids may be used as anhydride or in the form of an ester.
- use may be made of small amounts of unsaturated acids such as maleic acid, fumaric acid and itaconic acid.
- carboxylic acid there should be used orthohexahydrophthalic acid and/or the anhydride thereof and/or a homologue thereof, such as methylorthohexahydrophthalic acid.
- Incorporation of orthohexahydrophthalic acid units or a homologue of that acid into the oxidatively drying alkyd resin imparts excellent hydrolytic resistance to it; a far better resistance is obtained than upon the incorporation of phthalic acid, isophthalic acid, terephthalic acid or tetrahydrophthalic acid.
- the preferably employed di- or polyvalent carboxylic acids are generally used in an amount of 5 ⁇ 60 mole %, more particularly 10-55 mole %, of the total amount of carboxly group-containing compounds to be subjected to polycondensation.
- the di- or polyvalent carboxylic acids may be replaced in an amount of up to 50 mole % with aliphatic, cycloaliphatic and/or aromatic polyisocyanates, such as hexamethylene diisocyanate, isophoron diisocyanate or toluene diisocyanate.
- aromatic polyisocyanates such as hexamethylene diisocyanate, isophoron diisocyanate or toluene diisocyanate.
- the ionized, oxidatively drying alkyd resin contains one or more ethylenically unsaturated monocarboxylic acids, preferably polyunsaturated fatty acids having isolated double bonds, which acids generally contain 6-24 carbon atoms and occur in, int. al., linseed oil fatty acid, safflower oil fatty acid, soybean oil fatty acid and tall oil fatty acid. If desired, not more than 30% by weight of the fatty acid having isolated double bonds may be replaced with a fatty acid having such conjugated double bonds as occur in tung oil fatty acids and oiticica oil. If desired, the fatty acid may be used as such and/or in the form of a triglyceride.
- ethylenically unsaturated monocarboxylic acid use may be made of one or more saturated, aliphatic, cylcoaliphatic and/or aromatic monocarboxylic acids having 6-24 carbon atoms.
- monocarboxylic acids that are preferably used may be mentioned: benzoic acid, hexahydrobenzoic acid, 2-ethyl hexanoic acid, 2,5-dimethyl benzoic acid, p-tert. butyl benzoic acid and pivalic acid.
- the monocarboxylic acid is usually employed in an amount such that the ionized, oxidatively drying alkyd resin is built up of 25 ⁇ 85% by weight, preferably 35 ⁇ 75% by weight of such an acid.
- allylenically unsaturated monocarboxylic there may, if desired, also be used compounds which for instance have an allyl ether group.
- suitable allyl ether compounds include the allyl ethers of trimethylol propane, glycerol, pentaerythritol or sorbitol, and those of epoxy compounds, for instance: allyl glycidyl ether. These allyl compounds should contain at least one hydroxyl group or epoxy group. It is preferred that use should be made of a mono- or diallyl ether of trimethylol propane.
- the oxidatively drying alkyd resin is built up of 0-45% by weight of such an allyl compound.
- the oxidatively drying alkyd resin generally contains on average 2-20, preferably 2-12, oxidatively drying bonds per macromolecule.
- the ionized, oxidatively drying alkyd resin is further built up preferably of a dihydroxy carboxylic acid of the formula R-C(CH 2 0H) 2 -COOH, where R represents a hydrocarbon group having 1-14 carbon atoms and carrying an inert substituent or not, for instance an alkyl group having 1-4 carbon atoms, an aryl group having 6-14 carbon atoms, chloromethyl, nitropropyl or p-acetophenyl. It is preferred that use should be made of dimethylol propionic acid. It is preferred that the dihydroxy carboxylic acid should be used in an amount of 5-75 mole %, more particularly 10-60 mole %, of the total amount of the carboxyl group-containing compounds to be subjected to polycondensation.
- R represents a hydrocarbon group having 1-14 carbon atoms and carrying an inert substituent or not, for instance an alkyl group having 1-4 carbon atoms, an aryl group having 6-14 carbon atoms,
- the polycondensation reaction for preparing the ionized oxidatively drying alkyd resin is generally carried out at a temperature in the range of 140° to 300°C, preferably 180°-260°C, and in an inert atmosphere of, say, nitrogen and/or carbon dioxide.
- the water evolved during polycondensation may be removed in the usual manner, for instance by distillation under reduced pressure or by azeotropic distillation, using an organic solvent, for instance: toluene or xylene.
- the solvents may be removed, if desired, from the alkyd resin by distillation.
- the polycondensation reaction is continued until the alkyd resin has the desired acid number of 30-100, preferably 40-60, a hydroxyl number of 0-175, preferably 20-120, and a number average molecular weight of 1 000-12 000, preferably 2 000-8 000.
- a basic compound such as ammonia or a monoamine
- suitable amines may be mentioned the usual alkyl amines, cycloalkyl amines, heterocyclic amines and hydroxyl amines.
- the monoamines may be of a primary, a secondary or a tertiary nature. It is preferred that use should be made of tertiary alkyl amines having a boiling point below 150°C, for instance: triethylamine and dimethylisopropylamine.
- the aqueous solution of the ionized alkyd resin generally has a pH of 5-9.
- a water-miscible organic solvent Prior to ionization of the alkyd resin some desirable amount of a water-miscible organic solvent is usually added to it to set the viscosity and the rate of evaporation required upon application of the composition. It is preferred that the organic solvent should be used in an amount of 0-30% by weight, based on the total amount of solvent, including water.
- suitable organic solvents include: propanol, n-butanol, isobutanol, propoxypropanol, butoxyethanol, ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, and a monoalkyl ether, for instance: the methyl ether, the ethyl ether, the n-butyl ether or the isobutyl ether, of 1,2-propylene glycol.
- Preparation of the second binder component is carried out by polymerization of one or more monoethylenically unsaturated compounds in the presence of an aqueous solution of the afore-described ionized alkyd resin.
- Suitable monomers include aromatic compounds, such as styrene, vinyl toluene, a-methyl styrene; acrylic or methacrylic esters, such as methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-ethylhexyl acrylate, dodecyl acrylate and isobornyl (meth)-acrylate; nitriles, such as acrylonitrile and methacrylonitrile; and compounds such as vinyl chloride, vinyl acetate and vinyl propionate.
- aromatic compounds such as styrene, vinyl toluene, a-methyl styrene
- acrylic or methacrylic esters such as methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-ethylhe
- styrene and/or an acrylic or methacrylic ester of an alcohol having 1-24 carbon atoms such as methyl methacrylate, butyl acrylate, butyl methacrylate, lauryl methacrylate and stearyl acrylate.
- a.(3-monoethylenically unsaturated carboxylic acids for instance: acrylic acid, methacrylic acid, crotonic acid and maleic acid, may be copolymerized in small amounts of, say, 0,1-3% by weight, based on the total weight of the monomers.
- Tg glass transition temperature
- the weight ratio of the polymer obtained by polymerization to the ionized alkyd resin is generally such that the total binder system contains 15-75% by weight, preferably 20-60% by weight of the polymer and 20-80% by weight, preferably 30 ⁇ 70% by weight of the ionized alkyd resin, all percentages being based on the weight of the solid in the total binder system.
- Polymerization of the monomeric compound(s) takes place at a temperature of 30°-95°C, preferably 60°-85°C, in the presence of at least one radical initiator, optionally while use is made of ultraviolet radiation.
- at least one radical initiator optionally while use is made of ultraviolet radiation.
- radical initiators may be mentioned: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) benzoyl peroxide, tert. butyl peroctoate, methyl ethyl ketone peroxide, sodium persulphate and potassium persulphate.
- the initiator is usually employed in an amount of 0,2-6, preferably 0,5 ⁇ 4% by weight, based on the total weight of the monomers. If desired, the initiator may be added to the polymerization mixture batch-wise.
- the polymerization may be carried out by any usual method, for instance by gradually adding a mixture of the monomeric compound(s) and the radical initiator to an aqueous solution of the afore-described ionized, oxidatively drying alkyd resin.
- the aqueous solution of the oxidatively drying alkyd resin may also contain dispersed therein a third binder component, which will be described hereinafter in detail.
- the binder system contains as third component a dispersed, oxidatively drying alkyd resin having a number average molecular weight of 600-6 000, and acid number of 0-20 and a hydroxyl number of 0-130. It is preferred that the number average molecular weight, the acid number and the hydroxyl number have values of 800-4 000, 412 and 10-100, respectively.
- the viscosity of the dispersed alkyd resin as such is not higher than 30 Pa.s, preferably lower than 15 Pa.s measured at 20°C.
- the dispersed, oxidatively drying alkyd resin may be built up of components of the same groups of compounds as are used in the preparation of the ionized alkyd resin and they may be prepared in a similar manner. It is not necessary, however, for the two alkyd resins in one coating composition to be built up of exactly the same compounds.
- the preparation of the dispersed alkyd resin should, of course, be so carried out that a product is obtained which satisfies the afore-mentioned requirements and, moreover, is substantially built up of 3 ⁇ 40% by weight of a hydroxyl compound having 2 ⁇ 8 hydroxyl groups, 2 ⁇ 44% by weight of a di and/or multivalent carboxylic acid, of which 20 ⁇ 100 mole % is a cycloaliphatic dicarboxylic acid, and 20-90% by weight of an ethylenically unsaturated monocarboxylic acid having 6-24 carbon atoms.
- oxidatively drying alkyd resins there may optionally be chemically incorporated or physically mixed therewith such compounds as will cause degradation of coatings by incident sunlight to be considerably reduced.
- these compounds which may be present in an amount of 0,1-10% by weight, based on the alkyd resin, there may be mentioned compounds that have a benzotriazole or a benzophenone structure, such as 4,4'-dihydroxyethoxy-2,2'-dihydroxybenzophenone and/or aliphatic hydroxyl groups-containing derivatives of 2-(2-hydroxyphenyl)benzotriazole.
- the 3 binder components of the binder system according to the invention each have a calculated solubility parameter which differs from those of the two other components by not more than 1,7 units, the solubility parameter of the dispersed alkyd resin not being higher than 10,5.
- the binder system displays excellent mutual compatibility, resulting in a high degree of gloss of the coating upon application of the pigmented or non-pigmented coating composition obtained.
- the solubility parameters of the alkyd resins can be calculated using the constants of attraction of the separate groups, the specific gravity and the molecular weight [see J. Appl. Chem. 3,71 (1953)].
- the solubility parameter of the addition polymer is calculated by applying the equation where n is the number of moles of the monomeric compound, G the constant of molar attraction of the polymer unit and V m the molar volume of the polymer unit.
- the coating composition according to the invention may contain all kinds of additives, for instance: pigments, colourants, siccatives, dispersing agents, levelling agents, light stabilizers and fillers.
- additives for instance: pigments, colourants, siccatives, dispersing agents, levelling agents, light stabilizers and fillers.
- siccatives may be mentioned metal salts of (cyclo)aliphatic acids, such as octanoic acid, linoleic acid and naphthenic acid, examples of suitable metals including cobalt, manganese, lead, zirconium, calcium, zinc and rare earth metals. It is also possible to use mixtures of siccatives. Usually, the siccatives (calculated as metal) are applied in an amount of 0,001 to 0,5% by weight, calculated on the binder system as solid matter.
- the pigments, fillers and other adjuvants may be added to the aqueous coating composition directly and be dispersed therein under the influence of shearing forces.
- a pigment paste may be prepared which is based on at least part of the dispersed, water-undilutable, hardly or not water-ionizable alkyd resin to be used in the final coating composition, and the pigment paste thus prepared be added to the aqueous coating composition containing the other components of the binder system according to the invention.
- a pigment paste should be prepared which is based on part of the (non-pigmented) coating composition according to the invention and this pigment paste is subsequently added to the remaining amount of the coating composition, to which siccatives and other additives may have been beforehand, if desired.
- the coating composition is generally applied to a particular substrate by brushing or spraying, but some other method of application is also possible, of course.
- substrate there may be used a pretreated or non-pretreated metal, but preferably wood.
- the solids content is determined by heating the composition for 1 hour at 105°C in comformity with ASTM D 1650, the colour is determined by the Gardner 1933-scale and the viscosity with the aid of an Epprecht viscosity meter at 20°C and expressed in Pa.s.
- the values for the acid number and the hydroxyl number are given in mg KOH per gramme of solid resin. In the examples parts are parts by weight and % is per cent by weight, unless otherwise indicated.
- An oxidatively drying, water-dilutable alkyd resin was prepared in a reaction vessel equipped with a thermometer, a stirrer, a condenser and a separating vessel, by intermixing 188 g (0,650 moles) of tall oil fatty acid, 45,5 g (0,296 moles) of hexahydrophthalic anhydride, 139,3 g (1,040 moles) of dimethylol propionic acid, 14,5 g (0,108 moles) of trimethylol propane and 15,0 g of xylene. These compounds were heated to 225°C over a four-hour period and kept at that temperature until the reaction mixture had an acid number of 46.
- reaction mixture was cooled to 200°C and 15,3 g (0,100 moles) of hexahydrophthalic anhydride were added.
- the reaction mixture was kept at 200°C until the acid number thereof was 43.
- the xylene was removed from the reaction mixture under reduced pressure and after the mixture had been cooled to 150°C, 60,0 g of ethylene glycol monobutyl ether were added to it.
- the product obtained consisted of 240 g of a water-dilutable solution of an alkyd resin, the solution and the alkyd resin having the properties mentioned in Table 1.
- a water-insoluble, oxidatively drying alkyd resin was prepared in a reaction vessel according to Example A by intermixing therein 159,6 g (0,57 moles) of safflower oil fatty acid, 17,1 g (0,08 moles) of trimethylol propane diallyl ether, 33,1 g (0,215 moles) of hexahydrophthalic anhydride, 33,1 g (0,238 moles) of pentaerythritol and 8 g of xylene.
- a water-insoluble, oxidatively drying alkyd resin was prepared by intermixing 139,0 g (0,500 moles) of sunflower fatty acid, 31,3 g (0,233 moles) of trimethylol propane, 26,8 g (0,200 moles) of dimethylol propionic acid, 8,9 g (0,058 moles) of hexahydrophthalic anhydride, 11,8 g (0,061 moles) of trimellitic anhydide and 9,0 g of xylene.
- a water-insoluble, oxidatively drying alkyd resin was prepared by intermixing 135 g (0,482 moles) of tall oil fatty acid, 23,0 g (0,107 moles) of trimethylol propane diallyl ether, 32,4 g (0,234 moles) of pentaerythritol, 0,2 g (0,002 moles) of maleic anhydride, 29,6 g (0,200 moles) of phthalic anhydride, 9,2 g (0,060 moles) of hexahydrophthalic anhydride and 10,0 g of xylene.
- a water-insoluble, oxidatively drying alkyd resin was prepared by intermixing 140,7 g (0,503 moles) of soy bean oil fatty acid, 20,8 g (0,082 moles) of dipentaerythritol, 22,2 g (0,166 moles) of trimethylol propane and 10,0 g of xylene. The mixture was heated to 210°C over a period of 3 hours and kept at this temperature until the reaction mixture had an acid number of 8.
- aqueous dispersion was prepared by heating in it, with stirring, 475 parts of the alkyd resin solution according to Example A to 80°C, at which temperature the solution was neutralized with 31,6 parts of dimethylethanolamine. After 15 minutes there was gradually added a mixture of 34 parts of ethylene glycol monobutyl ether and 534 parts of demineralized water and a clear aqueous resin solution was obtained.
- Example D To the resulting dispersion there were subsequently added, with stirring 177 parts of the oxydatively drying alkyd resin according to Example D. There were obtained 1610 parts of a coating composition having a solids content of 54,8%, a viscosity of 8,63 Pa.s and a particle size of 250-1400 nm.
- Example E To the resulting dispersion there were subsequently added, with stirring 540 parts of the oxidatively drying alkyd resin according to Example E. There were obtained 2175 parts of a coating composition having a solids content of 62,1%, a viscosity of 11,34 Pa.s and a particle size of 250-1100 nm.
- Example 2 The procedure of Example 2 was repeated, except that the water-insoluble alkyd resin was added to the clear aqueous solution of the oxidatively drying alkyd resin before the monomeric compounds were added to the aqueous solution of the alkyd resin and polymerized. There were obtained 2175 parts of an aqueous coating composition having a solids content of 62,1%, a viscosity of 13,06 Pa.s and a particle size of 300-1200 nm.
- an aqueous dispersion was prepared by intermixing 547 parts of the alkyd resin solution according to Example C and 168 parts of ethylene glycol monobutyl ether and heating to 80°, with stirring. At this temperature the mixture was neutralized with 30 parts of dimethylethanolamine. After 15 minutes 915 parts of demineralized water were gradually added and a clear aqueous resin solution was obtained.
- Example F To the resulting dispersion there were subsequently added, with stirring 816,0 parts of the oxidatively drying alkyd resin according to Example F. There were obtained 2860 parts of a coating composition having a solids content of 56,9%, a viscosity of 3,62 Pa.s and a particle size of 300-1200.
- an aqueous dispersion was prepared by intermixing 653,0 parts of the alkyd resin solution according to Example A and 17,4 parts of ethylene glycol monobutyl ether and heating, with stirring, to 80°C. At this temperature the mixture was neutralized with 43,5 parts of dimethylethanolamine. After 15 minutes 586 parts of demineralized water were gradually added and a clear aqueous resin solution was obtained.
- the calculated value of the solubility parameter of the addition polymer was 9,41, the calculated glass transition temperature 18°C.
- 200,0 parts of the oxidatively drying alkyd resin according to Example D were obtained 1800 parts of a coating composition having a solids content of 55,5%, a viscosity of 13,8 Pa.s and a particle size of 200-1200 nm.
- Example 4 The procedure of Example 4 was repeated, with the exception that the monomer mixture used in the preparation of the addition polymer consisting of 50,0 parts of styrene, 342 parts of isobutyl methacrylate and 8,0 parts of methacrylic acid.
- the calculated value of the solubility parameter of the addition polymer was 9,04 and therefore 1,90 units below that of the water-dilutable alkyd resin.
- the calculated glass transition temperature of the addition polymer was 55°C.
- aqueous dispersion having a solids content of 39,2%, a viscosity of 3,24 Pa.s and a particle size of 250-1400 nm.
- the dispersion was applied to a glass plate to a layer thickness of 90 nm. After the coating had dried, it had a dull and inhomogeneous appearance.
- aqueous, non-pigmented coating compositions obtained in each of the Examples 1-6 first of all pigment pastes were prepared by intermixing the non-pigmented coating composition, water and butoxyethanol or 1-butoxy-2-propanol in the parts by weight mentioned in Table 3 and 70 parts of titanium dioxide (available under the trade mark of Kronos 2190 of Kronos Titan GmbH), 0,1 part of a defoaming agent (a modified polysiloxane copolymer available under the trade mark Byk VP 020 of Byk-Mallinckrodt) and 0,1 part of an anionic dispersing agent (based on unsaturated acid esters available under the trade mark Bykumen WS of Byk-Mallinckrodt) and grinding the mixture in a dispersing machine (commercially available under the trade mark Red Devil) to a pigment particle size not greater than 10 m.
- the resulting pigment pastes had a viscosity at 20°C of 40-50 sec (DIN cup No. 4).
- each of the pigment pastes was mixed with an amount, also mentioned in Table 3, of the non-pigmented coating composition corresponding to that of the example, to which 1 part of a siccative had been added.
- the siccative was a mixture of cobalt octoate, barium octoate and zirconium octoate (available under the trade mark Trockner 173 of Gebr. Borchers A.G.) containing 1,2% of cobalt, 7,2% of barium and 3,2% of zirconium (calculated as metal).
- the pigmented coating composition was made ready to be processed by adding the solvent in the amount mentioned in Table 3.
- the compositions had a solids content and a viscosity at 20°C (DIN cup No. 4) as indicated in Table 3.
- the resulting pigmented coating compositions were applied to a glass plate by means of a knife coater to a coating thickness of 40 IJm (after drying) and dried at a temperature of 23°C.
- the tack-free drying time was determined in accordance with DIN 53150 and of the coating the Persoz hardness (expressed in seconds) was measured after 24 and 72 hours, respectively, and the Gardner gloss at 60° and 20° (ASTM D 523).
- the resistance to water was measured in conformity with ASTM D 870-54. The rating "good” signifies that the coating has not undergone any visible change after 3 days' immersion in water of 37,8°C, followed by conditioning of the coating for 1 hour at 20°C.
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Abstract
Description
- The invention relates to an aqueous, oxidatively drying coating composition based on a binder system obtained by polymerization of one or more monoethylenically unsaturated compounds in the presence of an aqueous solution of an ionized, oxidatively drying alkyd resin.
- A coating composition of the type indicated above is known from US Patent Specification 4116 903. In actual practice, however, the gloss of the final coating and the brushability and properties such as hiding power, workability and filling of surface irregularities in the substrate, which are connected with a low solids content, are not quite satisfactory. An object of the present invention is to provide a coating composition which guarantees an optimum combination of said properties while retaining the other desired properties. Moreover, the composition may display a very good hydrolytic resistance.
- The coating composition according to the invention is characterized in that per 100 parts by weight (calculated on solid matter) the binder system also contains 5―65 parts by weight (calculated on solid matter) of a dispersed, oxidatively drying alkyd resin having a number average molecular weight in the range of 600-6 000, a viscosity not higher than 30 Pa.s, measured at 20°C, an acid number of 0-20 and a hydroxyl number of 0―130, which is substantially built up of 3―40% by weight of a hydroxyl compound having 2-8 hydroxyl groups, 2-44% by weight of a di- and/or multivalent carboxylic acid, of which 20-100 mole % is a cycloaliphatic dicarboxylic acid, and 20-90% by weight of an ethylenically unsaturated monocarboxylic acid having 6-24 carbon atoms.
- The ionized, oxidatively drying alkyd resin may be prepared by polycondensation of generally one or more aliphatic and/or cycloaliphatic di- and/or multivalent and, if desired, monovalent alcohols with one or more aliphatic, cycloaliphatic and/or aromatic di- and/or multivalent and, if desired, monovalent carboxylic acids, and/or derivatives of such alcohols or carboxylic acids, such as epoxy compounds, esters or acid anhydrides.
- Alcohols that are preferably used are the compounds of the formula HOCH2-CR,CR2-CH20H, where R1 represents a -CH20H group, a group R2 or an acryloyl group or methacryloyl group, and R2 represents a hydrocarbon group carrying an inert substituent or not, for instance an alkyl group having 1-4 carbon atoms, an aryl group having 6-14 carbon atoms, chloromethyl, nitropropyl or p-acetophenyl. Representative alcohols that are preferably used are: trimethylol ethane, trimethylol propane, trimethylol butane, 2,2-dimethyl-1,3-propane diol, 2-methyl-2-propyl-1,3-propane diol, 2-ethyl-2-butyl-1,3-propane diol and 2-methyl-2-phenyl-1,3-propane diol. More particularly, use is made of trimethylol propane. The preferably employed alcohols are generally used in an amount of 2-98 mole %, more particularly 2-90 mole %, of the total amount of hydroxyl group-containing compounds to be subjected to polycondensation. Examples of suitable alcohols further include: 1,2-propylene glycol, propylene oxide, 1,4-dimethylol cylcohexane, perhydrobisphenol, glycerol, glycidol, pentaerythritol and etherification products of polyvalent alcohols, for instance: di-, tri-, tetra- and a polypentaerythritol.
- As examples of suitable di- or polyvalent carboxylic acids may be mentioned: succinic acid, adipic acid, trimethyl adipic acid, sebacic acid, dimerised fatty acids, tetrahydrophthalic acid, 3,6-endomethylene tetrahydrophthalic acid, 3,6-endomethylene cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid or a homologue thereof, 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, orthophthalic acid, isophthalic acid, terephthalic acid and trimellitic acid. If desired, one or more of these acids may be used as anhydride or in the form of an ester. Optionally, use may be made of small amounts of unsaturated acids such as maleic acid, fumaric acid and itaconic acid. It is preferred that as carboxylic acid there should be used orthohexahydrophthalic acid and/or the anhydride thereof and/or a homologue thereof, such as methylorthohexahydrophthalic acid. Incorporation of orthohexahydrophthalic acid units or a homologue of that acid into the oxidatively drying alkyd resin imparts excellent hydrolytic resistance to it; a far better resistance is obtained than upon the incorporation of phthalic acid, isophthalic acid, terephthalic acid or tetrahydrophthalic acid. The preferably employed di- or polyvalent carboxylic acids are generally used in an amount of 5―60 mole %, more particularly 10-55 mole %, of the total amount of carboxly group-containing compounds to be subjected to polycondensation. Optionally, the di- or polyvalent carboxylic acids may be replaced in an amount of up to 50 mole % with aliphatic, cycloaliphatic and/or aromatic polyisocyanates, such as hexamethylene diisocyanate, isophoron diisocyanate or toluene diisocyanate.
- In order to obtain the oxidatively drying character the ionized, oxidatively drying alkyd resin contains one or more ethylenically unsaturated monocarboxylic acids, preferably polyunsaturated fatty acids having isolated double bonds, which acids generally contain 6-24 carbon atoms and occur in, int. al., linseed oil fatty acid, safflower oil fatty acid, soybean oil fatty acid and tall oil fatty acid. If desired, not more than 30% by weight of the fatty acid having isolated double bonds may be replaced with a fatty acid having such conjugated double bonds as occur in tung oil fatty acids and oiticica oil. If desired, the fatty acid may be used as such and/or in the form of a triglyceride.
- Besides the ethylenically unsaturated monocarboxylic acid use may be made of one or more saturated, aliphatic, cylcoaliphatic and/or aromatic monocarboxylic acids having 6-24 carbon atoms. As examples of monocarboxylic acids that are preferably used may be mentioned: benzoic acid, hexahydrobenzoic acid, 2-ethyl hexanoic acid, 2,5-dimethyl benzoic acid, p-tert. butyl benzoic acid and pivalic acid. The monocarboxylic acid is usually employed in an amount such that the ionized, oxidatively drying alkyd resin is built up of 25―85% by weight, preferably 35―75% by weight of such an acid. Besides the ethylenically unsaturated monocarboxylic there may, if desired, also be used compounds which for instance have an allyl ether group. Examples of suitable allyl ether compounds include the allyl ethers of trimethylol propane, glycerol, pentaerythritol or sorbitol, and those of epoxy compounds, for instance: allyl glycidyl ether. These allyl compounds should contain at least one hydroxyl group or epoxy group. It is preferred that use should be made of a mono- or diallyl ether of trimethylol propane. Generally, the oxidatively drying alkyd resin is built up of 0-45% by weight of such an allyl compound. The oxidatively drying alkyd resin generally contains on average 2-20, preferably 2-12, oxidatively drying bonds per macromolecule.
- The ionized, oxidatively drying alkyd resin is further built up preferably of a dihydroxy carboxylic acid of the formula R-C(CH20H)2-COOH, where R represents a hydrocarbon group having 1-14 carbon atoms and carrying an inert substituent or not, for instance an alkyl group having 1-4 carbon atoms, an aryl group having 6-14 carbon atoms, chloromethyl, nitropropyl or p-acetophenyl. It is preferred that use should be made of dimethylol propionic acid. It is preferred that the dihydroxy carboxylic acid should be used in an amount of 5-75 mole %, more particularly 10-60 mole %, of the total amount of the carboxyl group-containing compounds to be subjected to polycondensation.
- The polycondensation reaction for preparing the ionized oxidatively drying alkyd resin is generally carried out at a temperature in the range of 140° to 300°C, preferably 180°-260°C, and in an inert atmosphere of, say, nitrogen and/or carbon dioxide. The water evolved during polycondensation may be removed in the usual manner, for instance by distillation under reduced pressure or by azeotropic distillation, using an organic solvent, for instance: toluene or xylene. Upon completion of the polycondensation the solvents may be removed, if desired, from the alkyd resin by distillation.
- The polycondensation reaction is continued until the alkyd resin has the desired acid number of 30-100, preferably 40-60, a hydroxyl number of 0-175, preferably 20-120, and a number average molecular weight of 1 000-12 000, preferably 2 000-8 000. Subsequently, at least part, preferaby 50-100%, of the acid groups of the alkyd resin is neutralized with a basic compound, such as ammonia or a monoamine, to ionize the oxidatively drying alkyd resin, in order that the alkyd resin may be satisfactorily soluble in water. As suitable amines may be mentioned the usual alkyl amines, cycloalkyl amines, heterocyclic amines and hydroxyl amines. The monoamines may be of a primary, a secondary or a tertiary nature. It is preferred that use should be made of tertiary alkyl amines having a boiling point below 150°C, for instance: triethylamine and dimethylisopropylamine. The aqueous solution of the ionized alkyd resin generally has a pH of 5-9.
- Prior to ionization of the alkyd resin some desirable amount of a water-miscible organic solvent is usually added to it to set the viscosity and the rate of evaporation required upon application of the composition. It is preferred that the organic solvent should be used in an amount of 0-30% by weight, based on the total amount of solvent, including water. Examples of suitable organic solvents include: propanol, n-butanol, isobutanol, propoxypropanol, butoxyethanol, ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, and a monoalkyl ether, for instance: the methyl ether, the ethyl ether, the n-butyl ether or the isobutyl ether, of 1,2-propylene glycol.
- Preparation of the second binder component is carried out by polymerization of one or more monoethylenically unsaturated compounds in the presence of an aqueous solution of the afore-described ionized alkyd resin.
- Examples of suitable monomers include aromatic compounds, such as styrene, vinyl toluene, a-methyl styrene; acrylic or methacrylic esters, such as methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-ethylhexyl acrylate, dodecyl acrylate and isobornyl (meth)-acrylate; nitriles, such as acrylonitrile and methacrylonitrile; and compounds such as vinyl chloride, vinyl acetate and vinyl propionate. It is preferred that use should be made of styrene and/or an acrylic or methacrylic ester of an alcohol having 1-24 carbon atoms, such as methyl methacrylate, butyl acrylate, butyl methacrylate, lauryl methacrylate and stearyl acrylate. If desired, a.(3-monoethylenically unsaturated carboxylic acids, for instance: acrylic acid, methacrylic acid, crotonic acid and maleic acid, may be copolymerized in small amounts of, say, 0,1-3% by weight, based on the total weight of the monomers. If desired, also other monomers may be used, for instance compounds having an oxidatively drying group such as acrylic or methacrylic esters of oleyl alcohol or linoleyl alcohol, fatty acid esters of hydroxyalkyl (meth)acrylates, dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate. It is preferred that the monomers and the ratios between them should so be chosen that the calculated glass transition temperature (Tg) of the prepared polymer as such is in the range of -30°C to 120°C and preferably between -10° and 80°C.
- The weight ratio of the polymer obtained by polymerization to the ionized alkyd resin is generally such that the total binder system contains 15-75% by weight, preferably 20-60% by weight of the polymer and 20-80% by weight, preferably 30―70% by weight of the ionized alkyd resin, all percentages being based on the weight of the solid in the total binder system.
- Polymerization of the monomeric compound(s) takes place at a temperature of 30°-95°C, preferably 60°-85°C, in the presence of at least one radical initiator, optionally while use is made of ultraviolet radiation. Generally, use is made of initiators having a half-life period such at the chosen polymerization temperature that a certain amount of initiator is present throughout the polymerization reaction.
- As examples of suitable radical initiators may be mentioned: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) benzoyl peroxide, tert. butyl peroctoate, methyl ethyl ketone peroxide, sodium persulphate and potassium persulphate. The initiator is usually employed in an amount of 0,2-6, preferably 0,5―4% by weight, based on the total weight of the monomers. If desired, the initiator may be added to the polymerization mixture batch-wise. The polymerization may be carried out by any usual method, for instance by gradually adding a mixture of the monomeric compound(s) and the radical initiator to an aqueous solution of the afore-described ionized, oxidatively drying alkyd resin. According to the present invention the aqueous solution of the oxidatively drying alkyd resin may also contain dispersed therein a third binder component, which will be described hereinafter in detail.
- According to the invention the binder system contains as third component a dispersed, oxidatively drying alkyd resin having a number average molecular weight of 600-6 000, and acid number of 0-20 and a hydroxyl number of 0-130. It is preferred that the number average molecular weight, the acid number and the hydroxyl number have values of 800-4 000, 412 and 10-100, respectively.
- The viscosity of the dispersed alkyd resin as such is not higher than 30 Pa.s, preferably lower than 15 Pa.s measured at 20°C.
- The dispersed, oxidatively drying alkyd resin may be built up of components of the same groups of compounds as are used in the preparation of the ionized alkyd resin and they may be prepared in a similar manner. It is not necessary, however, for the two alkyd resins in one coating composition to be built up of exactly the same compounds. The preparation of the dispersed alkyd resin should, of course, be so carried out that a product is obtained which satisfies the afore-mentioned requirements and, moreover, is substantially built up of 3―40% by weight of a hydroxyl compound having 2―8 hydroxyl groups, 2―44% by weight of a di and/or multivalent carboxylic acid, of which 20―100 mole % is a cycloaliphatic dicarboxylic acid, and 20-90% by weight of an ethylenically unsaturated monocarboxylic acid having 6-24 carbon atoms.
- Moreover, in one or in both oxidatively drying alkyd resins there may optionally be chemically incorporated or physically mixed therewith such compounds as will cause degradation of coatings by incident sunlight to be considerably reduced. As examples of these compounds, which may be present in an amount of 0,1-10% by weight, based on the alkyd resin, there may be mentioned compounds that have a benzotriazole or a benzophenone structure, such as 4,4'-dihydroxyethoxy-2,2'-dihydroxybenzophenone and/or aliphatic hydroxyl groups-containing derivatives of 2-(2-hydroxyphenyl)benzotriazole.
- The 3 binder components of the binder system according to the invention each have a calculated solubility parameter which differs from those of the two other components by not more than 1,7 units, the solubility parameter of the dispersed alkyd resin not being higher than 10,5. As a result, the binder system displays excellent mutual compatibility, resulting in a high degree of gloss of the coating upon application of the pigmented or non-pigmented coating composition obtained. The solubility parameters of the alkyd resins can be calculated using the constants of attraction of the separate groups, the specific gravity and the molecular weight [see J. Appl. Chem. 3,71 (1953)]. The solubility parameter of the addition polymer is calculated by applying the equation
- Optionally, the coating composition according to the invention may contain all kinds of additives, for instance: pigments, colourants, siccatives, dispersing agents, levelling agents, light stabilizers and fillers.
- As examples of suitable siccatives may be mentioned metal salts of (cyclo)aliphatic acids, such as octanoic acid, linoleic acid and naphthenic acid, examples of suitable metals including cobalt, manganese, lead, zirconium, calcium, zinc and rare earth metals. It is also possible to use mixtures of siccatives. Usually, the siccatives (calculated as metal) are applied in an amount of 0,001 to 0,5% by weight, calculated on the binder system as solid matter.
- The pigments, fillers and other adjuvants may be added to the aqueous coating composition directly and be dispersed therein under the influence of shearing forces. Alternatively, first a pigment paste may be prepared which is based on at least part of the dispersed, water-undilutable, hardly or not water-ionizable alkyd resin to be used in the final coating composition, and the pigment paste thus prepared be added to the aqueous coating composition containing the other components of the binder system according to the invention. It is preferred, however, that first a pigment paste should be prepared which is based on part of the (non-pigmented) coating composition according to the invention and this pigment paste is subsequently added to the remaining amount of the coating composition, to which siccatives and other additives may have been beforehand, if desired.
- In actual practice the coating composition is generally applied to a particular substrate by brushing or spraying, but some other method of application is also possible, of course. As substrate there may be used a pretreated or non-pretreated metal, but preferably wood.
- The invention will be further described in but not limited by the following examples. In them, unless otherwise indicated, the solids content is determined by heating the composition for 1 hour at 105°C in comformity with ASTM D 1650, the colour is determined by the Gardner 1933-scale and the viscosity with the aid of an Epprecht viscosity meter at 20°C and expressed in Pa.s. The values for the acid number and the hydroxyl number are given in mg KOH per gramme of solid resin. In the examples parts are parts by weight and % is per cent by weight, unless otherwise indicated.
- An oxidatively drying, water-dilutable alkyd resin was prepared in a reaction vessel equipped with a thermometer, a stirrer, a condenser and a separating vessel, by intermixing 188 g (0,650 moles) of tall oil fatty acid, 45,5 g (0,296 moles) of hexahydrophthalic anhydride, 139,3 g (1,040 moles) of dimethylol propionic acid, 14,5 g (0,108 moles) of trimethylol propane and 15,0 g of xylene. These compounds were heated to 225°C over a four-hour period and kept at that temperature until the reaction mixture had an acid number of 46. Subsequently, the xylene was removed from the reaction mixture under reduced pressure and after the mixture had been cooled to 150°C, 119 g of ethylene glycol monobutyl ether were added to it. There were obtained 475 g of a water-dilutable solution of an alkyd resin, with the solution and the alkyd resin having the properties mentioned in Table 1.
- In the reaction vessel according to Example A an oxidatively drying, water-dilutable alkyd resin was prepared by intermixing 89,60 g (0,320 moles) of safflower oil fatty acid, 13,86 g (0,090 moles) of hexahydrophthalic anhydride, 67,00 g (0,500 moles) of dimethylol propionic acid, 2,0 g (0,015 moles) of trimethylol propane and 5,0 g of xylene.
- These compounds were heated to 230°C over a period of 3) hours, at which temperature they were kept until the reaction mixture had an acid number of 45. Subsequently, the xylene was removed from the reaction mixture under reduced pressure and after the mixture had been cooled to 150°C, 53 g of ethylene glycol monobutyl ether were added to it. There were obtained 211 g of a water-dilutable solution of an alkyd resin, with the solution and the alkyd resin having the properties mentioned in Table 1.
- In the reaction vessel according to Example A an oxidatively drying, water-dilutable alkyd resin was prepared by intermixing 44,7 g (0,160 moles) of linseed oil fatty acid, 44,8 g (0,160 moles) of sunflower oil fatty acid, 34,7 g (0,136 moles) of dipentaerythritol and 6,0 g of xylene. The mixture was heated to 230°C over a period of 4 hours and kept at this temperature until the reaction mixture had an acid number of 9. Subsequently, 12,5 g (0,093 moles) of trimethylol propane, 31,8 g (0,215 moles) of phthalic anhydride and 6,7 g (0,050 moles) of dimethylol propionic acid were added to the reaction mixture. The reaction mixture was again heated to 230°C over a period of H hours and kept at this temperature until the reaction mixture had an acid number of 21. On the strength of the degree of polycondensation corresponding to the acid number of 21 and the difference in reactivity between the primary carboxyl groups of the phthalic acid and the tertiary carboxyl groups of the dimethylol propionic acid it is assumed that practically all of the phthalic anhydride has undergone polycondensation.
- Next, the reaction mixture was cooled to 200°C and 15,3 g (0,100 moles) of hexahydrophthalic anhydride were added. The reaction mixture was kept at 200°C until the acid number thereof was 43. Finally, the xylene was removed from the reaction mixture under reduced pressure and after the mixture had been cooled to 150°C, 60,0 g of ethylene glycol monobutyl ether were added to it. The product obtained consisted of 240 g of a water-dilutable solution of an alkyd resin, the solution and the alkyd resin having the properties mentioned in Table 1.
- A water-insoluble, oxidatively drying alkyd resin was prepared in a reaction vessel according to Example A by intermixing therein 159,6 g (0,57 moles) of safflower oil fatty acid, 17,1 g (0,08 moles) of trimethylol propane diallyl ether, 33,1 g (0,215 moles) of hexahydrophthalic anhydride, 33,1 g (0,238 moles) of pentaerythritol and 8 g of xylene.
- These compounds were heated to 230°C over a period of 4 hours and kept at this temperature until the reaction mixture had an acid number of 8. Subsequently, the xylene was removed from the reaction mixture under reduced pressure. The product obtained consisted of 229 g of an alkyd resin having the properties mentioned in Table 2.
- In the reaction vessel according to Example A a water-insoluble, oxidatively drying alkyd resin was prepared by intermixing 139,0 g (0,500 moles) of sunflower fatty acid, 31,3 g (0,233 moles) of trimethylol propane, 26,8 g (0,200 moles) of dimethylol propionic acid, 8,9 g (0,058 moles) of hexahydrophthalic anhydride, 11,8 g (0,061 moles) of trimellitic anhydide and 9,0 g of xylene.
- These compounds were heated to 240°C over a period of 3) hours and kept at this temperature until the reaction mixture had an acid number of 12,5. Subsequently, the xylene was removed from the reaction mixture under reduced pressure. There were obtained 204 g of an alkyd resin having the properties mentioned in Table 2.
- In the reaction vessel according to Example A a water-insoluble, oxidatively drying alkyd resin was prepared by intermixing 135 g (0,482 moles) of tall oil fatty acid, 23,0 g (0,107 moles) of trimethylol propane diallyl ether, 32,4 g (0,234 moles) of pentaerythritol, 0,2 g (0,002 moles) of maleic anhydride, 29,6 g (0,200 moles) of phthalic anhydride, 9,2 g (0,060 moles) of hexahydrophthalic anhydride and 10,0 g of xylene. These compounds were heated to 240°C over a period of 3) hours and kept at this temperature until the reaction mixture had an acid number of 10,0. Subsequently, the xylene was removed from the reaction mixture under reduced pressure. There were obtained 217 g of an alkyd resin having the properties mentioned in Table 2.
- In the reaction vessel according to Example A a water-insoluble, oxidatively drying alkyd resin was prepared by intermixing 140,7 g (0,503 moles) of soy bean oil fatty acid, 20,8 g (0,082 moles) of dipentaerythritol, 22,2 g (0,166 moles) of trimethylol propane and 10,0 g of xylene. The mixture was heated to 210°C over a period of 3 hours and kept at this temperature until the reaction mixture had an acid number of 8.
- Subsequently, 26,7 g (0,124 moles) of trimethylol propane diallyl ether, 12,7 g (0,086 moles) of phthalic anhydride, 7,6 g (0,050 moles) of hexahydrophthalic anhydride and 14,5 g (0,075 moles) of trimellitic anhydride were added to the reaction mixture. Next, the reaction mixture was heated to 240°C over a period of 2 hours and kept at this temperature until the reaction mixture had an acid number of 8. Then the xylene was removed from the reaction mixture under reduced pressure. There was obtained 230 g of an alkyd resin having the properties mentioned in Table 2.
- In a reaction vessel equipped with a thermometer and a stirrer an aqueous dispersion was prepared by heating in it, with stirring, 475 parts of the alkyd resin solution according to Example A to 80°C, at which temperature the solution was neutralized with 31,6 parts of dimethylethanolamine. After 15 minutes there was gradually added a mixture of 34 parts of ethylene glycol monobutyl ether and 534 parts of demineralized water and a clear aqueous resin solution was obtained. To this solution there was added at 80°C over a period of 2 hours a mixture consisting of 43,1 parts of styrene, 125,0 parts of methyl methacrylate, 176,8 parts of butyl methacrylate, 5,3 parts of methacrylic acid and 10,0 parts of 2,2'-azobisisobutyronitrile. Two hours after termination of the addition of the monomer initiator mixture another 3,5 parts of the initiator were added and the polymerization thereof was continued for 4 hours at 80°C. The calculated value of the solubility parmeter of the addition polymer was 9,65, the calculated glass transition temperature 56°C. There were obtained 1433 parts of a stable aqueous dispersion having a solids content of 49,3% and a viscosity of 9,75 Pa.s.
- To the resulting dispersion there were subsequently added, with stirring 177 parts of the oxydatively drying alkyd resin according to Example D. There were obtained 1610 parts of a coating composition having a solids content of 54,8%, a viscosity of 8,63 Pa.s and a particle size of 250-1400 nm.
- In the reaction vessel according to Example 1 491 parts of the alkyd resin solution according to Example B were heated, with stirring, to 80°C, at which temperature the solution was neutralized with 25 parts of dimethylethanolamine. After 15 minutes there was gradually added a mixture of 54 parts of ethylene glycol monobutyl ether and 620 parts of demineralized water and a clear aqueous solution was obtained. Over a period of 3 hours and at a temperature of 80°C there was added to this solution a mixture of 320 parts of butyl methacrylate, 113 parts of methyl methacrylate, 7 parts of methacrylic acid and 8,4 parts of 2,2'-azobisisobutyronitrile. Three hours after termination of the addition of the monomer-initiator mixture 4,2 parts of the initiator were added and the polymerization reaction was thereafter continued for 4 hours at 80°C. The calculated value of the solubility parameter of the addition polymer was 9,56, the calculated glass transition temperature 40-C. There were obtained 1635 parts of a stable, aqueous dispersion having a solids content of 49,6% and a viscosity of 14,52 Pa.s.
- To the resulting dispersion there were subsequently added, with stirring 540 parts of the oxidatively drying alkyd resin according to Example E. There were obtained 2175 parts of a coating composition having a solids content of 62,1%, a viscosity of 11,34 Pa.s and a particle size of 250-1100 nm.
- The procedure of Example 2 was repeated, except that the water-insoluble alkyd resin was added to the clear aqueous solution of the oxidatively drying alkyd resin before the monomeric compounds were added to the aqueous solution of the alkyd resin and polymerized. There were obtained 2175 parts of an aqueous coating composition having a solids content of 62,1%, a viscosity of 13,06 Pa.s and a particle size of 300-1200 nm.
- In a reaction vessel fitted with a thermometer and a stirrer an aqueous dispersion was prepared by intermixing 547 parts of the alkyd resin solution according to Example C and 168 parts of ethylene glycol monobutyl ether and heating to 80°, with stirring. At this temperature the mixture was neutralized with 30 parts of dimethylethanolamine. After 15 minutes 915 parts of demineralized water were gradually added and a clear aqueous resin solution was obtained. Over a period of 2 hours and at a temperature of 80°C there was added to this solution a mixture of 80,0 parts of styrene, 112,0 parts of methyl methacrylate, 200,0 parts of butyl methacrylate, 8,0 parts of methacrylic acid and 8,0 parts of 2,2-azobisisobutyronitrile. Subsequently, 3 hours after termination of the addition of the monomer-initiator mixture another4 parts of the initiator were added and the polymerization reaction was thereafter continued for 4 hours at 80°C. The calculated value of the solubility parameter of the addition polymer was 9,61, the calculated glass transition temperature 56°C.
- There were obtained 2050 parts of a stable aqueous dispersion having a solids content of 39,8% and a viscosity of 2,51 Pa.s.
- To the resulting dispersion there were subsequently added, with stirring 816,0 parts of the oxidatively drying alkyd resin according to Example F. There were obtained 2860 parts of a coating composition having a solids content of 56,9%, a viscosity of 3,62 Pa.s and a particle size of 300-1200.
- In a reaction vessel equipped with a thermometer and a stirrer an aqueous dispersion was prepared by intermixing 653,0 parts of the alkyd resin solution according to Example A and 17,4 parts of ethylene glycol monobutyl ether and heating, with stirring, to 80°C. At this temperature the mixture was neutralized with 43,5 parts of dimethylethanolamine. After 15 minutes 586 parts of demineralized water were gradually added and a clear aqueous resin solution was obtained.
- Over a period of 2 hours and at a temperature of 80°C there was added to this solution a mixture of 98,0 parts of styrene, 92,0 parts of butyl methacrylate, 24,5 parts of methyl methacrylate, 26 parts of 2-hydroxypropyl methacrylate, 61,0 parts of linoleyl acrylate, 4,6 parts of methacrylic acid and 10,0 parts of 2,2'-azobisisobutyronitrile. Subsequently, 2 hours after termination of the addition of the monomer-initiator mixture another 3,5 parts of the initiator were added and the polymerization reaction was continued for 4 hours at 80°C. The calculated value of the solubility parameter of the addition polymer was 9,41, the calculated glass transition temperature 18°C. There were obtained 1600 parts of a stable aqueous dispersion having a solids content of 50,1 % and a viscosity of 10,29 Pa.s. To the resulting dispersion there were subsequently added, with stirring, 200,0 parts of the oxidatively drying alkyd resin according to Example D. There were obtained 1800 parts of a coating composition having a solids content of 55,5%, a viscosity of 13,8 Pa.s and a particle size of 200-1200 nm.
- In a reaction vessel fitted with a thermometer and a stirrer 600 parts of an alkyd resin solution according to Example B were heated, with stirring, to 80°C, at which temperature the solution was neutralized with 30,6 parts of dimethylethanolamine.
- After 15 minutes a mixture of 27 parts of 1-butoxy-2-propanol and 620 parts of demineralized water were gradually added and a clear aqueous resin solution was obtained.
- Over a period of 3 hours and at a temperature of 80°C there was added to this solution a mixture of 108,0 parts of styrene, 72,0 parts of methyl methacrylate, 175,0 parts of butyl methacrylate, 5,0 parts of methacrylic acid and 6,0 parts of 2,2'-azobisisobutyronitrile. Subsequently, 3 hours after termination of the addition of the monomer-initiator mixture another 3,0 parts of the initiator were added and the polymerization reaction was continued for 4 hours at 80°C. The calculated value of the solubility parameter of the addition polymer was 9,57, the calculated glass transition temperature 57°C. There were obtained 1640 parts of a stable aqueous dispersion having a solids content of 49,8% and a viscosity of 7,93 Pa.s.
- To the resulting dispersion there were subsequently added, with stirring, 272 parts of the oxidatively drying alkyd resin according to Example G. There were obtained 1912 parts of a coating composition having a solids content of 56,9%, a viscosity of 9,22 Pa.s and a particle size of 200-1000 nm.
- The procedure of Example 4 was repeated, with the exception that the monomer mixture used in the preparation of the addition polymer consisting of 50,0 parts of styrene, 342 parts of isobutyl methacrylate and 8,0 parts of methacrylic acid. The calculated value of the solubility parameter of the addition polymer was 9,04 and therefore 1,90 units below that of the water-dilutable alkyd resin. The calculated glass transition temperature of the addition polymer was 55°C.
- There were obtained 2048 parts of an aqueous dispersion having a solids content of 39,2%, a viscosity of 3,24 Pa.s and a particle size of 250-1400 nm. The dispersion was applied to a glass plate to a layer thickness of 90 nm. After the coating had dried, it had a dull and inhomogeneous appearance.
- From the aqueous, non-pigmented coating compositions obtained in each of the Examples 1-6 first of all pigment pastes were prepared by intermixing the non-pigmented coating composition, water and butoxyethanol or 1-butoxy-2-propanol in the parts by weight mentioned in Table 3 and 70 parts of titanium dioxide (available under the trade mark of Kronos 2190 of Kronos Titan GmbH), 0,1 part of a defoaming agent (a modified polysiloxane copolymer available under the trade mark Byk VP 020 of Byk-Mallinckrodt) and 0,1 part of an anionic dispersing agent (based on unsaturated acid esters available under the trade mark Bykumen WS of Byk-Mallinckrodt) and grinding the mixture in a dispersing machine (commercially available under the trade mark Red Devil) to a pigment particle size not greater than 10 m. The resulting pigment pastes had a viscosity at 20°C of 40-50 sec (DIN cup No. 4).
- Subsequently, each of the pigment pastes was mixed with an amount, also mentioned in Table 3, of the non-pigmented coating composition corresponding to that of the example, to which 1 part of a siccative had been added. The siccative was a mixture of cobalt octoate, barium octoate and zirconium octoate (available under the trade mark Trockner 173 of Gebr. Borchers A.G.) containing 1,2% of cobalt, 7,2% of barium and 3,2% of zirconium (calculated as metal). After the pigment paste had been added, the pigmented coating composition was made ready to be processed by adding the solvent in the amount mentioned in Table 3. The compositions had a solids content and a viscosity at 20°C (DIN cup No. 4) as indicated in Table 3.
- The resulting pigmented coating compositions were applied to a glass plate by means of a knife coater to a coating thickness of 40 IJm (after drying) and dried at a temperature of 23°C. The tack-free drying time was determined in accordance with DIN 53150 and of the coating the Persoz hardness (expressed in seconds) was measured after 24 and 72 hours, respectively, and the Gardner gloss at 60° and 20° (ASTM D 523). Of the coating also the resistance to water was measured in conformity with ASTM D 870-54. The rating "good" signifies that the coating has not undergone any visible change after 3 days' immersion in water of 37,8°C, followed by conditioning of the coating for 1 hour at 20°C.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT82201642T ATE16400T1 (en) | 1981-12-29 | 1982-12-21 | AQUEOUS COATING AGENTS DRYING BY OXIDATION. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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NL8105879 | 1981-12-29 | ||
NL8105879 | 1981-12-29 |
Publications (2)
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EP0083137A1 EP0083137A1 (en) | 1983-07-06 |
EP0083137B1 true EP0083137B1 (en) | 1985-11-06 |
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ID=19838625
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EP82201642A Expired EP0083137B1 (en) | 1981-12-29 | 1982-12-21 | Aqueous, oxidatively drying coating composition |
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US (1) | US4447567A (en) |
EP (1) | EP0083137B1 (en) |
JP (1) | JPS58118863A (en) |
AT (1) | ATE16400T1 (en) |
AU (1) | AU554011B2 (en) |
CA (1) | CA1190339A (en) |
DE (1) | DE3267330D1 (en) |
ES (1) | ES518611A0 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007048189A1 (en) * | 2007-10-08 | 2009-04-09 | Evonik Röhm Gmbh | Aqueous dispersions comprising at least one alkyd resin and at least one polymer having at least one (meth) acrylate segment |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3524337A1 (en) * | 1985-07-08 | 1987-01-08 | Roehm Gmbh | MEDICINAL PACKAGING |
US4616062A (en) * | 1985-10-21 | 1986-10-07 | Owens-Corning Fiberglas Corporation | Polyester emulsion |
AU586517B2 (en) * | 1985-10-29 | 1989-07-13 | Nippon Shokubai Kagaku Kogyo Kabushiki Kaisha | Low-shrinkage unsaturated polyester composition |
AT387971B (en) * | 1986-11-14 | 1989-04-10 | Vianova Kunstharz Ag | METHOD FOR PRODUCING WATER-DETERMINABLE AIR-DRYING LACQUER AND THE USE THEREOF |
US4912187A (en) * | 1988-01-29 | 1990-03-27 | Questra Chemicals Corp. | Solid ester products of sterically hindered polyhydroxymonocarboxylic acids |
US4978741A (en) * | 1988-01-29 | 1990-12-18 | Questra Chemicals Corp. | Method for preparing essentially haze-free isophthalic acid- and polymethylolalkanoic acid-containing resins |
US5096959A (en) * | 1990-03-06 | 1992-03-17 | The Valspar Corporation | Hydrolysis resistant alkyl resin coating composition |
US5055548A (en) * | 1990-10-11 | 1991-10-08 | Westvaco Corporation | Sovlent-borne alkyd resin compositions |
EP0555903A1 (en) * | 1992-02-04 | 1993-08-18 | Akzo Nobel N.V. | Water-dispersible hybrid core-shell polymer, an aqueous dispersion thereof, and a coating composition made therefrom |
US5356973A (en) * | 1992-08-31 | 1994-10-18 | Ppg Industries, Inc. | Aqueous based coating compositions having improved metallic pigment orientation |
ES2103536T3 (en) * | 1993-01-21 | 1997-09-16 | Akzo Nobel Nv | AQUEOUS POLYMER DISPERSIONS OF AIR DRYING. |
US6518338B2 (en) | 2001-05-08 | 2003-02-11 | Basf Corporation | Fast drying alkyd basecoat refinish composition |
US6794442B2 (en) | 2001-06-21 | 2004-09-21 | Basf Corporation | Fast drying basecoat refinish composition |
BRPI0413319B1 (en) * | 2003-08-08 | 2014-12-23 | Ici Plc | “AUTO-OXIDABLE ARCHITECTURAL COATING COMPOSITION” |
US7470751B2 (en) * | 2004-09-21 | 2008-12-30 | Basf Corporation | Stabilized water-borne polymer compositions for use as water-based coatings |
US8097575B2 (en) * | 2004-12-02 | 2012-01-17 | Harris Research, Inc. | Composition and method for cleaning and neutralizing a surface |
DE102005049402A1 (en) * | 2005-10-13 | 2007-04-19 | Basf Ag | Aqueous binder composition |
WO2008124725A1 (en) * | 2007-04-10 | 2008-10-16 | Biopreserve Llc | Soy- based coating |
WO2008152078A1 (en) * | 2007-06-15 | 2008-12-18 | Basf Se | Low-voc aqueous hybrid binder |
US8070189B2 (en) * | 2007-06-20 | 2011-12-06 | Carefusion 303, Inc. | Safety luer connection |
DE102008046075A1 (en) | 2008-09-08 | 2010-03-11 | Evonik Röhm Gmbh | (Meth) acrylate monomer, polymer and coating agent |
DE102009026820A1 (en) | 2008-09-08 | 2010-03-11 | Evonik Röhm Gmbh | Functionalized (meth) acrylate monomer, polymer, coating agent and method of preparation and crosslinking |
JP5451025B2 (en) * | 2008-10-10 | 2014-03-26 | 関西ペイント株式会社 | One-component water-based paint composition for construction machinery or industrial machinery |
US8337995B2 (en) | 2008-12-19 | 2012-12-25 | Valspar Sourcing, Inc. | Low penetration low formaldehyde alkyd composition |
EP2508555B1 (en) | 2011-03-21 | 2015-05-13 | Electrolux Home Products Corporation N.V. | Process for producing pre-expandable plastic beads and beads obtainable according to said process |
WO2015019898A1 (en) * | 2013-08-07 | 2015-02-12 | Dic株式会社 | Active energy ray-curable resin composition, undercoating agent containing same, and molded article |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2851430A (en) * | 1953-12-11 | 1958-09-09 | Northrop Aircraft Inc | Film-forming compositions from oiticica oil modified and styrenated alkyds |
US3428586A (en) * | 1965-09-21 | 1969-02-18 | Ashland Oil Inc | Water dispersible coating composition and use of same in electrocoat painting |
US4094836A (en) * | 1975-03-26 | 1978-06-13 | Sumitomo Chemical Company, Limited | Aqueous alkyd resins |
US4116903A (en) * | 1977-03-02 | 1978-09-26 | P.R.A. Laboratories Incorporated | Alkyd-supported emulsion interpolymers and methods for preparation |
JPS53132093A (en) * | 1977-04-22 | 1978-11-17 | Kansai Paint Co Ltd | Oxidatively crosslinking type rapid drying water-soluble resin composition |
US4293471A (en) * | 1979-03-16 | 1981-10-06 | E. I. Du Pont De Nemours And Company | Fast-drying alkyd latex |
-
1982
- 1982-12-21 DE DE8282201642T patent/DE3267330D1/en not_active Expired
- 1982-12-21 EP EP82201642A patent/EP0083137B1/en not_active Expired
- 1982-12-21 AT AT82201642T patent/ATE16400T1/en not_active IP Right Cessation
- 1982-12-23 AU AU91826/82A patent/AU554011B2/en not_active Ceased
- 1982-12-23 CA CA000418506A patent/CA1190339A/en not_active Expired
- 1982-12-27 US US06/452,927 patent/US4447567A/en not_active Expired - Lifetime
- 1982-12-28 ES ES518611A patent/ES518611A0/en active Granted
- 1982-12-28 JP JP57234966A patent/JPS58118863A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007048189A1 (en) * | 2007-10-08 | 2009-04-09 | Evonik Röhm Gmbh | Aqueous dispersions comprising at least one alkyd resin and at least one polymer having at least one (meth) acrylate segment |
Also Published As
Publication number | Publication date |
---|---|
US4447567A (en) | 1984-05-08 |
DE3267330D1 (en) | 1985-12-12 |
JPH0244344B2 (en) | 1990-10-03 |
ES8308903A1 (en) | 1983-10-01 |
ATE16400T1 (en) | 1985-11-15 |
AU9182682A (en) | 1983-07-07 |
JPS58118863A (en) | 1983-07-15 |
CA1190339A (en) | 1985-07-09 |
AU554011B2 (en) | 1986-08-07 |
ES518611A0 (en) | 1983-10-01 |
EP0083137A1 (en) | 1983-07-06 |
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